The present invention relates to novel 1-arylpyrazole hydroxylamines, hydrazines, and compositions containing them. The invention particularly pertains to compositions of said compounds and methods and use of said compounds for the control of arthropod, nematode, helminth or protozoan pests, in particular to the application of said compounds or compositions in agricultural methods of use, particularly as pesticides, for controlling arthropods, especially insects by systemic action.
The control of insects, nematodes or helminths by means of an active ingredient having a 1-arylpyrazole group therein has been described in such patent applications such as International Patent Publication No. WO 93/06089, WO 94/21606 and WO 87/03781 as well as in European Patent Publication Numbers 0295117, 659745, 679650, 201852 and 412849, German Patent No. DE 19511269 and U.S. Pat. No. 5,232,940.
Other compounds are disclosed in WO 92/13451, Aug. 20 1992, to Schering Agrochemicals Ltd., which describes 5-chloro-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(4,5-1H-pyrazole as an intermediate, also with activity against a single species Lucilia sericata, sleep blow fly.
This Schering reference appears to be the only reference describing 1-arylpyrazole-oxime compounds as insecticides.
It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.
A second object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, plant nematodes, or helminth or protozoan pests, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.
A third object of the present invention is to provide very active compounds, with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal and nematicidal, systemic, antifeeding or pesticidal activity via seed treatment.
A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages.
A fifth object of the present invention is to provide compounds with greatly improved (greater and faster) penetration into pest species when topically applied and thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest.
Another object of the present invention is to provide compounds with high activity and improved safety to the user and the environment.
These and other objects of the invention shall become readily apparent from the detailed description of the present invention.
These objects are met in whole or in part by the instant invention.
The present invention provides arylpyrazoles of formula (I): 
wherein:
A is xe2x80x94Oxe2x80x94 or xe2x80x94NR8;
Y is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, xe2x80x94S(O)mR10, xe2x80x94P(O)R11R12, xe2x80x94P(S)R12, xe2x80x94Si(R13)(R14)(R15), xe2x80x94C(O)R9, xe2x80x94C(S)R9, cyano or nitro;
R1 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl;
R2 is xe2x80x94S(O)nR16 or alkyl or haloalkyl;
R3 is hydrogen, halogen, xe2x80x94C(O)R17, xe2x80x94S(O)pR18, alkyl, haloalkyl, xe2x80x94OR19, xe2x80x94Nxe2x95x90C(R20)(R21),alkenyl, xe2x80x94NR22R23, 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, or xe2x80x94CHxe2x95x90NOH;
R4, R5 and R7 are independently selected from hydrogen, halogen or alkyl;
R6 is halogen, haloalkyl, haloalkoxy, xe2x80x94S(O)qR24 or SF5;
R8 is hydrogen or substituted or unsubstituted alkyl;
R9 is hydrogen, substituted or unsubstituted alkyl of C1 to C20, substituted or unsubstituted aryl, xe2x80x94OR25, xe2x80x94NR26R27, or and xe2x80x94SR28;
R10 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl;
R11 and R12 are independently selected from alkoxy and thioalkoxy;
R13, R14 and R15 are independently selected from alkyl, haloalkyl and aryl;
R16 is alkyl, alkenyl, alkynyl, or C3-C6 cycloalkyl each of which is optionally substituted by one or more halogen;
R17 is hydrogen, alkyl, alkoxy or thioalkoxy;
R18 is alkyl, haloalkyl or aryl;
R19 and R20 are independently selected from hydrogen, alkyl and haloalkyl;
R21 is alkyl, alkoxy or phenyl each of which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, xe2x80x94CN, alkyl, xe2x80x94S(O)s-alkyl;
R22 and R23 are independently selected from hydrogen, NH2, xe2x80x94S(O)rR29, xe2x80x94C(O)R30, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl and alkynyl; or R22 and R23 may form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur;
R24 is haloalkyl;
R25 and R28 are independently selected from substituted or unsubstituted alkyl and substituted and unsubstituted aryl;
R26 and R27 are independently selected from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; R26 and R27 may form together a divalent alkylene radical which may be interrupted by one or more heteroatoms preferably selected from oxygen, nitrogen and sulfur;
R29 is substituted or unsubstituted alkyl;
R30 is hydrogen, alkyl, haloalkyl, aryl, alkenyl, xe2x80x94OR31, xe2x80x94SR31, or xe2x80x94NR32R33;
R31 is alkyl or haloalkyl;
R32 and R33 are independently selected from hydrogen, alkyl, haloalkyl and aryl;
Z is hydrogen, substituted or unsubstituted alkyl, xe2x80x94S(O)tR34, xe2x80x94C(O)R35, xe2x80x94P(O)R36R37, xe2x80x94P(S)R36R37, cyano or nitro;
R34 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl;
R35 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, xe2x80x94OR38, xe2x80x94NR39R40 or xe2x80x94SR41;
R36 and R37 are independently selected from alkoxy, haloalkoxy, thioalkoxy and haiothioalkoxy;
R38 and R41 are independently selected from substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;
R39 and R40 are independently selected from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; or R39 and R40 may form together a divalent alkylene radical which may be interrupted by one or more heteroatoms preferably selected from oxygen, nitrogen and sulfur;
m, n, p, q, r, s, and t independently represent zero, one or two;
M is C-halo, Cxe2x80x94CH3, Cxe2x80x94CH2F, Cxe2x80x94CH2Cl, Cxe2x80x94NO2, or N;
or a pesticidally acceptable salt thereof.
By the term xe2x80x9cpesticidally acceptable saltsxe2x80x9d is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed by compounds of formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable salts formed with bases from compounds of formula (I) include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.
Preferably by the term xe2x80x9csubstitutedxe2x80x9d is meant substituted by one or more of the following substituents: halogen, hydroxy, alkoxy, alkylthio, cyano, carboxy, alkyl, haloalkyl, xe2x80x94C(O)alkyl, xe2x80x94C(O)O-alkyl, xe2x80x94C(O)NH2, xe2x80x94C(O)NH-alkyl, xe2x80x94C(O)N(alkyl)2, aryl, nitro, azido, amino, alkylamino, dialkylamino, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, aryloxy, arylthio, alkylcarbonylamino, alkylcarbonyloxy, or aryloxycarbonyl.
Unless otherwise specified, alkyl groups and moieties including them have from one to six, preferably one to four, carbon atoms, alkenyl groups have from two to six, preferably two to four, carbon atoms, and alkynyl groups have from three to six, preferably three to four carbon atoms. By the term xe2x80x9carylxe2x80x9d is meant mono or polycyclic aromatic moieties including phenyl, pyridyl, pyrimidinyl and naphthyl groups. The term xe2x80x9chaloxe2x80x9d before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br or I, in any combination, preferably F or Cl. The term xe2x80x9chalogenxe2x80x9d means F, Cl, Br or I. It shall be understood that the rings formed by the divalent alkylene radicals represented by R25 and R26, R26 and R27, or R39 and R40 and including the nitrogen atoms to which they are attached are generally 5, 6 and 7-membered rings.
A preferred class of arylpyrazoles of formula (I) are those with one or more of the following features wherein:
A is xe2x80x94Oxe2x80x94 or xe2x80x94NR8xe2x80x94;
Y is H or substituted or unsubstituted alkyl;
R1 is substituted or unsubstituted alkyl;
R2 is S(O)nR18;
R3 is xe2x80x94NR25R26;
R4 is halo;
R5 and R7 are hydrogen;
R6 is haloalkyl;
M is C-halo; or
Z is hydrogen or substituted or unsubstituted alkyl
Another preferred class of 1-arylpyrazoles of formula (I) is one wherein:
A is xe2x80x94Oxe2x80x94;
Y is hydrogen;
R1 is alkyl, preferably methyl;
R2 is S(O)alkyl, preferably SOMe or SOEt;
R3 is xe2x80x94NH2;
R4 is Cl;
R5 and R7 are hydrogen;
R6 is CF3;
M is Cxe2x80x94Cl; and
Z is hydrogen.
Another preferred class of 1-arylpyrazoles of formula (I) is one wherein:
A is xe2x80x94NR8xe2x80x94;
Y is hydrogen;
R1 is alkyl, preferably methyl;
R2 is S(O)alkyl, preferably SOMe or SOEt;
R3 is xe2x80x94NH2;
R4 is xe2x80x94Cl;
R5 and R7 are hydrogen;
R6 is CF3;
M is Cxe2x80x94Cl; and
Z is hydrogen.
Preferred aryl groups comprising the R4 to R7 and M radicals in formula (I) are: 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro-4-trifluoromethoxyphenyl; 2-bromo-6-chloro-4-trifluoromethylphenyl; 2-bromo-6-chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl;2-chloro-4-trifluoromethylphenyl; 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl; and 2,6-dichloro-4-pentafluorothiophenyl.
Specifically preferred compounds according to the invention are:
1) 5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-N-hydroxy-N-methyl-1H-pyrazole carboximidamide (mp about 190xc2x0 C.)
2) 5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfinyl-N-hydroxy-N-methyl-1H-pyrazole carboximidamide (mp about 156xc2x0 C.).
According to a further feature of the invention, compounds of general formula (I) are prepared by reacting, compounds of formula (II): 
with a compound of formula (III): 
in which Y and A are defined above. The reaction is generally performed using an acid salt of a compound of formula (III), for example the hydrochloride salt, and in the presence of a base for example pyridine or an alkali metal carbonate (such as sodium carbonate) or an alkali metal acetate (such as sodium acetate) or ammonium acetate in a solvent such as methanol and/or water at a temperature from 0xc2x0 C. to 100xc2x0 C.
According to a further feature of the present invention compounds of general formula (I) wherein Z is H may be prepared by the reaction of a compound of formula (IV): 
wherein R represents alkyl with a compound of formula (III). The reaction is generally performed using an acid salt of a compound of formula (III), for example the hydrochloride salt, and optionally in the presence of a base (for example pyridine or an alkali metal carbonate such as sodium carbonate) or an alkali metal acetate (such as sodium acetate or ammonium acetate) in a solvent such as methanol and/or water and generally at a temperature from 0xc2x0 C. to 100xc2x0 C.
According to a further feature of the invention, compounds of formula (I) wherein Y is xe2x80x94S(O)mR10, xe2x80x94P(O)R11R12, xe2x80x94P(S)R11R12, xe2x80x94Si(R13)(R14)(R15), xe2x80x94C(O)R9, xe2x80x94C(S)R9, cyano or nitro may be prepared by reaction of a compound of formula (I) wherein Y is hydrogen, with sulfenylating, sulfinylating, sulfonating phosphorylating, thiophosphorylating, silylating, acylating or thioacylating, cyanating, or nitrating reagent, respectively, generally in the presence of bas such as triethylamine or sodium carbonate and generally in a solvent at a temperature generally in the range xe2x88x92100 to 100xc2x0 C.
According to a further feature of the invention, compounds of formula (I) wherein Z is substituted or unsubstituted alkyl, xe2x80x94S(O)tR34, xe2x80x94C(O)R35, xe2x80x94P(O)R36R37, xe2x80x94P(S)R36R37, cyano or nitro may be prepared by:
a) reaction of a compound of formula (IV) with alkylating, sulfenylating, sulfinylating, sulfonating, phosphorylating, thiophosphonylating, acylating, cyanating or nitrating reagent, respectively, generally in the presence of a base such as triethylamine or sodium carbonate and generally in a solvent at a temperature generally in the range from xe2x88x92100 to 100xc2x0 C.; and
b) reaction with a compound of formula (III).
The compounds of formula (II) wherein R2, R3, R4, R5, R6 and M are the above described substituents can be prepared by methods described in one or more of the following: WO 94/21606, WO 93/06089, WO 87/03781, WO 97/22593; European Patent Publications EP 0295117, EP 0511845, EP 0403309, EP 0403300, EP 352944, EP 780378; U.S. Pat. Nos. 5,232,940, 5,047,550, 4,918,085; German Patent Publication No. 19511269; or by methods known to the skilled in the art.
The synthesis of higher oxidation states of the compounds of formula (I), i.e., compounds in which m, n, p, q, r, and s are 1 or 2, can be achieved by oxidation of the corresponding compounds in which those variables are 0 or 1.
Intermediates of formula (II) may be prepared by known methods (see for example the above listed references).
Certain compounds of formula (II) are novel and as such constitute a further feature of the invention.
Intermediates of formula (IV) wherein R represents alkyl may be prepared by the reaction of compounds of formula (II) with an alcohol of formula ROH where R is alkyl. The alcohol is usually employed in excess as the solvent but a co-solvent such as tetrahydrofuran may be present. The reaction is generally carried out in the presence of a base such as sodium alkoxide at a temperature of from 0xc2x0 C. to 100xc2x0 C.
Compounds of formula (IV) are novel and as such constitute a further feature of the invention.
Intermediates of formula (III) are known or may be prepared by known methods.
The following Example illustrates detailed methods of synthesis and their physical properties of representative pesticidal compounds of formula (I) according to the invention.